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    • 专利摘要:
    FLUOROURETANS AS ADDITIVES IN A PHOTOPOLYMER FORMULATION. The invention relates to a photopolymer formulation comprising matrix polymers, recording monomers and photoinitiators, the use of the photopolymer formulation for the production of optical elements, in particular for the production of holographic elements and images, a process for lighting holographic media from photopolymer formulation, as well as special fluorourethanes.
    公开号:BR112012010471B1
    申请号:R112012010471-3
    申请日:2010-11-02
    公开日:2020-10-20
    发明作者:Thomas Rölle；Friedrich-Karl Bruder；Thomas Fäcke；Marc-Stephan Weiser；Dennis Hönel
    申请人:Bayer Materialscience Ag；
    IPC主号:
    专利说明:

    The invention relates to a photopolymer formulation comprising matrix polymers, recording monomers and photoinitiators, to the use of the photopolymer formulation for the production of optical elements, in particular for the production of holographic elements and images, a process for exposure holographic media for the formulation of photopolymers under light, as well as special fluorourethanes.
    WO 2008/125229 A1 describes photopolymer formulations of the type described at the beginning. These comprise matrix polymers based on polyurethane, etching monomers based on acrylic, as well as photoinitiators. In a hardened state, the recording monomers and photoinitiators are physically distributed in the polyurethane matrix. This WO also describes the addition of dibutyl phthalate, a classic plasticizer for technical plastics, to the photopolymer formulation.
    For the use of photopolymer formulations in the fields of application described below, the modulation of the Δn refractive index, generated by the holographic exposure in the photopolymer, plays a fundamental role. During holographic exposure, the interference field of the reference and signal light beam (in the simplest case, of two plane waves) is reproduced by a network of the refractive index through the spatial photopolymerization of, for example, highly refractive acrylates in high intensity spaces in the interference field. The refractive index network in photopolymers (the hologram) contains information about the signal light beam. Exposing the hologram only with the reference light beam allows the signal to be reconstructed again. The signal strength thus reconstructed in relation to the radiation strength of the reference light is called diffraction efficiency, hereinafter referred to in this document as DE (Diffraction Efficiency). In the simplest case of a hologram formed from the overlap of two plane waves, the DE is obtained from the quotients of the intensity of the diffracted light during the reconstruction and from the sum of the radiation intensities of the reference light and of the diffracted light. The higher the DE, the more efficient a hologram is in relation to the amount of light required from the reference light, which is needed to make the signal visible with fixed clarity. Highly refractive acrylates are able to create networks of high amplitude refractive indexes between the areas with the lowest refractive index and the areas with the highest refractive index to thereby allow holograms with high DE and high Δn in formulations photopolymers. It is necessary to note that the DE depends on the product of Δn and on the density of photopolymer d. The larger the product, the greater the ED possible (for reflection holograms). The width of the angle area at which the hologram becomes visible (reconstructed), for example, with monochromatic lighting depends on the density d. With hologram lighting with, for example, white light, the width of the spectral area that contributes to the reconstruction of the hologram may also depend only on the density d. The following is valid here: the lower the d, the greater the respective acceptance widths. If the goal is to produce clearer and only slightly visible holograms, a high Δn-d and a reduced d density are required in order to achieve a possibly high ED. This means, the greater Δn, the greater the freedom to create clearer holograms by adjusting d without loss of DE. Therefore, Δn optimization in the optimization of photopolymer formulations is of fundamental importance (P. Hariharan, Optical Holography, 2nd Edition, Cambridge University Press, 1996.).
    The task of the present invention is to provide a photopolymer formulation, which in comparison with the known formulations allows the production of holograms with a higher clarity.
    This task is achieved with the photopolymer formulation according to the invention through the plasticizer containing fluorourethanes. In this way, it was discovered that the addition of fluorourethanes to the known photopolymer formulations produces high Δn values in the formed holograms. In terms of results, this means that the holograms produced from the formulations according to the invention have a higher clarity compared to the known holograms.
    As for fluorourethanes, these are preferably compounds that have a structural element of the general formula (I)
    and which are replaced by at least one fluorine atom.
    Most preferred are fluorourethanes that have the general formula (II)
    in which n≥1 and ≤8 and R1, R2, R3 are hydrogen and / or linear, branched, cyclic or heterocyclic organic radicals that are not substituted or possibly substituted by hetero atoms, independent of each other, in which at least one of the radicals R1, R2 , R3 is replaced by at least one fluorine atom. Especially preferred, it is an organic radical R1 with at least one fluorine atom.
    According to another embodiment, R1 can comprise 1 -20 CF2 groups and / or one or more CF3 groups, especially preferred 1-15 CF2 groups and / or one or more CF3 groups, particularly preferably 1-10 CF2 groups and / or one or more CF3 groups, even more preferably 1-8 CF2 groups and / or one or more CF3 groups, R2 may comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, particularly A C1-C10 alkyl or hydrogen radical is preferred, and / or R3 can comprise a C1-C20 alkyl radical, preferably a C1-C15 alkyl radical, especially preferred a C1-C10 alkyl or hydrogen radical.
    Especially preferred are fluorourethanes that have structural elements of uretdione, isocyanurate, biuret, allophanate, polyurea, oxadiazadione and / or iminooxadiazindione or mixtures of these structural elements.
    Fluorourethanes may especially have a n20D refractive index of ≤ 1,4600, preferably ≤ 1,4500, particularly preferably ≤ 1,4400 and even more preferred ≤ 1,4300.
    Fluorourethanes may have a fluorine content of 10-80% by weight of fluorine, preferably 12.5-75% by weight of fluorine, especially preferred 15-70% by weight of fluorine and particularly preferably 17, 5-65% by weight of fluorine.
    The fluorourethanes of formula (III) can be obtained by reacting isocyanates of formula R [NCO] n with fluorinated alcohols under stoichiometric conditions under the formation of urethane.
    Preferred isocyanates of the formula R [NCO] n are methyl isocyanates, ethyl isocyanates, isomeric propyl isocyanates, isomeric butyl isocyanates, isomeric pentyl isocyanates, isomeric hexyl isocyanates, isylic isocyanates, octyl isocyanates, isomeric nonyl, isomeric decyl isocyanates, stearyl isocyanate, cyclopropyl isocyanate, cyclobutyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, cycloheptyl isocyanate, 2-methylpentane-1.5 diisocyanate diisocyanate, diisate, diisate, diis , 8-diisocyanate-4- (isocyanatomethyl) octane (TIN), 6-diisocyanatohexane (HDI, Desmodur H), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI, Desmodur I), 2 , 4,4-trimethylhexanes- 1,6-diisocyanate (TMDI), dicyclohexylmethane diisocyanate (Desmodur W), hexahydrotoluylene diisocyanate (H6TDI), bis (cyclohexyl 4-isocyanate) -methane (H12-MDI), 1,3 -bis- (methyl isocyanate) -cyclohexane, Desmodur LD, De smodur N 100, Desmodur N3200, Desmodur N3300, Desmodur N3350, Desmodur N3368, Desmodur N3375, Desmodur N3390, Desmodur N3400, Desmodur N3600, Desmodur N3790, Desmodur N3800, Desmodur N3900, Desmodur N50, Desmodur375, Desmodur375, Desmodur1 PL350, Desmodur PM76, Desmodur BL3175, Desmodur BL3272, Desmodur BL3370, Desmodur BL475, Desmodur BL4265, Desmodur BL5375, Desmodur BLXP2677, Desmodur DA-L, Desmodur DN, Desmodur E 305, Desmodur E3265, Desmodur O33A, Bayon Desmodur O33A, Bay 2078/2, Desmodur VP LS 2114/1, Desmodur VP LS 2257, Desmodur VP LS 2352/1, Desmodur VP LS 2371, Desmodur VP LS 2376/1, Desmodur XP 2406, Desmodur XP 2489, Desmodur XP 2565, Desmodur XP 2580 , Desmodur XP 2599, Desmodur XP 2617, Desmodur XP 2626, Desmodur XP 2675, Desmodur XP 2679, Desmodur XP 2714, Desmodur XP 2730, Desmodur XP 2731, Desmodur XP 2742, Desmodur XP 2748, Desmodur Z 4470 or their mixtures.
    Especially preferred isocyanates of the formula R [NCO] are isomeric propyl isocyanates, isomeric butyl isocyanates, isomeric pentyl isocyanates, isomeric hexyl isocyanates, isomeric heptyl isocyanates, isomeric octyl isocyanates, isyl ocyl isocyanates isomeric, isomeric decyl isocyanates, stearyl isocyanates, 1,8-diisocyanate-4- (isocyanatomethyl) octane (TIN), hexane 6-diisocyanate (HDI, Desmodur H), 1-isocyanate-3,3,5 -trimethyl-5-isocyanatomethyl-cyclohexane (IPDI, Desmodur I), 2,4,4-trimethylhexanes-1,6-diisocyanate (TMDI), dicyclohexylmethane-diisocyanate (Desmodur W), hexahydrotoluylene diisocyanate (H6TDI), 1,3 -bis- (isocyanatometil) -cyclohexane, Desmodur LD, Desmodur N3400, Desmodur N3600, Baymicron OXA or their mixtures.
    Even more preferred isocyanates of the formula R [NCO] are isopropyl isocyanates, n-butyl isocyanates, n-hexyl isocyanates, n-octyl isocyanates, n-decyl isocyanates, cyclohexyl isocyanates, stearyl isocyanates, 1,8 - diisocyanato-4- (isocyanatometil) octane (TIN), 6-diisocyanatohexane (HDI, Desmodur H), 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI, Desmodur I), 2,4 , 4-trimethylhexane-1,6-diisocyanate (TMDI), dicyclohexylmethane-diisocyanate (Desmodur W), hexahydrotoluylene diisocyanate (H6TDI), 1,3-bis- (isocyanatomethyl) -cyclohexane, Desmodur LD, Desmodur N3400, Desmodur N3600, Desmodur N3600, Desmodur Desmodur N3900, Baymicron OXA or their mixtures.
    The selection of fluorinated alcohols is wide, but preferably primary or secondary, mono, di or trifunctional alcohols with a fluorine content of 30% to 82% fluorine are used, especially preferred from 40% to 80% fluorine and particularly preferred from 49% to 75% fluorine.
    As for the reaction of isocyanates with alcohols of the types mentioned above for the production of fluorourethanes, this is a urethanization. The reaction can take place with the help of known catalysts to accelerate isocyanate addition reactions, such as, for example, tertiary amines, tin, zinc, iron or bismuth compounds, especially triethylamine, 1,4-diazabicycl- [2,2 , 2] - octane, bismuth octoate, zinc octoate or tin dibutyl dilaurate, which can be previously introduced or dosed later.
    Fluorourethanes may have a content of isocyanate groups (M = 42 g / mol) or free isocyanate monomers of less than 0.5% by weight, preferably less than 0.2% by weight, particularly preferably less than 0, 1% by weight.
    In addition, fluorourethane may have contents of unreacted hydroxyfunctional compounds of less than 1% by weight, preferably less than 0.5% by weight and especially preferred less than 0.2% by weight.
    Fluorourethanes may have a fluorine content of 10-80% by weight of fluorine, preferably 12.5-75% by weight of fluorine, especially preferred 15-70% by weight of fluorine and particularly preferably 17, 5-65% by weight of fluorine.
    Fluorourethanes may especially have a n20D refractive index of <1,4600, preferably <1,4500, particularly preferably <1,4400 and even more preferably <1,4300.
    During the production of fluorourethanes, isocyanates and alcohols can be dissolved respectively in a non-reactive solvent, such as, for example, an aromatic or aliphatic hydrocarbon or an aromatic or aliphatic halogenated hydrocarbon or a paint solvent, such as, for example, ethyl acetate or butyl acetate or acetone or butanone or an ether such as tetrahydrofuran or tert-butyl-methyl-ether or a dipolar-aprotic solvent such as, for example, dimethylshoxide or N-methylpyrrolidone or N-ethylpyrrolidone and can be previously introduced or dosed according to the method known to those skilled in the art.
    At the end of the reaction, the non-reactive solvents can be removed from the mixture under normal pressure or under reduced pressure and the final product can be determined by means of the solids content. The solids contents are normally in the range of 99.999 to 95.0% by weight, preferably from 99.998 to 98.0% by weight in relation to fluorourethane.
    As for matrix polymers, these can be especially polyurethanes. Preferably, polyurethanes are obtained by reacting an isocyanate component a) with an isocyanate-reactive component b).
    The isocyanate component a) preferably comprises polyisocyanates.
    As polyisocyanates, all compounds or mixtures known to those skilled in the art can be used, which present on average two or more NCO functions per molecule. These can be aromatic, araliphatic, aliphatic or cycloaliphatic based. In secondary amounts, monoisocyanates and / or polyisocyanates containing unsaturated groups can also be used.
    Suitable are, for example, butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanate-4- (isocyanatomethyl) -octane, 2,2,4- and / or 2,4 , 4-trimethylhexamethylene-diisocyanate, isomeric bis- (4,4'-isocyanatocyclohexyl) methanes and the isomer content of their mixtures, isocyanatomethyl-1,8-octanodiisocyanate, 1,4-cyclohexylenediisocyanate, cyclohexanedimethylates -phenylenediisocyanate, 2,4- and / or 2,6-toluylenediisocyanate, 1,5-naphthylenediisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate and / or triphenylmethane-4,4 ', 4 "-triisocyanate.
    It is also possible to employ derivatives of monomeric di or triisocyanates with structures of urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazintrione, uretdione and / or iminooxadiazindione.
    Preferably, polyisocyanates based on aliphatic and / or cycloaliphatic di or triisocyanates are used.
    Preferably, the polyisocyanates of components a) are aliphatic di or triisocyanates and / or cycloaliphatic di or oligomerized.
    Particularly preferably, isocyanurates, uretdiones and / or iminooxadiazindiones based on HDI, 1,8-diisocyanate-4- (isocyanatomethyl) -octane or mixtures thereof are used.
    They can also be used as components a) NCO-functional prepolymers with urethane, allophanate, biuret and / or amide groups. The prepolymers of components a) are obtained by methods well known to those skilled in the art through the reaction of monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in appropriate stoichiometry under optional use of catalysts and solvents.
    As polyisocyanates a1), all aliphatic, cycloaliphatic, aromatic or araliphatic di and triisocyanates known to those skilled in the art are suitable, in which it is irrelevant, whether these were obtained through phosgenation or through a phosgene-free process. In addition, high molecular weight reaction products well known to those skilled in the art obtained from monomeric di and / or triisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazintrione, uretdione can also be used. , iminooxadiazindione, either individually or mixed together as desired.
    Some examples of suitable monomeric di or triisocyanates that can be used as components a1) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-diisocyanate-4- (isocyanatomethyl) -octane, isocyanate-methyl-1,8-octanodiisocyanate (TIN), 2,4- and / or 2,6-toluene-diisocyanate.
    As isocyanate-reactive compounds a2) for the formation of prepolymers, functional OH compounds are preferably employed. These are analogous to OH-functional compounds as described below for components b).
    Equally possible is the application of amines for the production of prepolymers. For example, ethylenediamine, diethylene triamine, triethylene tetramine, propylene diamine, diaminocyclohexane, diaminobenzyl, diaminobisphenyl, difunctional polyamines, such as, for example, Jeffamine®, aminoterminated polymers with average molar masses up to 10000 g / mol, or mixtures of their mixtures .
    For the production of prepolymers containing biuret groups, excess isocyanate is reacted with amine, in which a biuret group is formed. As amines are suitable, in this case for the reaction with the mentioned di, tri and polyisocyanates, all oligomeric or polymeric amines, primary or secondary, difunctional of the type mentioned above.
    Preferred prepolymers are urethanes, allophanates or biurets of functional isocyanate aliphatic compounds and isocyanate-reactive oligomeric or polymeric compounds with average molar masses of 200 to 10000 g / mol, especially preferred are urethanes, allophanates or biurides of functional isocyanate aliphatic compounds and polyols oligomeric or polymeric or polyamines with average molar masses of 500 to 8500 g / mol and particularly preferred are HDI or TMDI allophanates and difunctional polyether polyols with average molar masses of 1000 to 8200 g / mol.
    Preferably, the prepolymers described above have levels of free monomeric isocyanate radicals less than 1% by weight, especially preferred less than 0.5% by weight, particularly preferably less than 0.2% by weight.
    Naturally, the isocyanate component can contain proportionally in addition to the prepolymers described, other isocyanate components. Here, aromatic, araliphatic, aliphatic and cycloaliphatic di, tri or polyisocyanates must also be taken into account. Mixtures of such di, tri or polyisocyanates can also be employed. Examples of suitable di, tri or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanate-4- (isocyanatomethyl) octane, 2,2,4- and / or 2 , 4,4-trimethylhexamethylenediisocyanate (TMDI), the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and the isomer content of their mixtures, isocyanatomethyl-1,8-octanodiisocyanate, 1,4-cyclohexylenediisocyanate, cyclohexanisyls , 4-phenylenediisocyanate, 2,4- and / or 2,6-toluylenediisocyanate, 1,5-naphthylene-diisocyanate, 2,4'- or 4,4'-diphenylmethanediisocyanate, triphenylmethane-4,4 ', 4 "-triisocyanate or its derivatives with structures of urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazintrione, uretdione, iminooxadiazindione and mixtures thereof. Preferably, the polyisocyanates based on oligomerized diisocyanates and / or derivatized in diocyanates which have been released in diocyanates which have been released in diocyanates excess through appropriate methods, especially especially those of hexamethylene diisocyanate. Especially preferred are oligomeric isocyanurates, HDI uretdiones and iminooxadiazindiones as well as mixtures thereof.
    Eventually it is also possible that the components of isocyanates a) may proportionally contain isocyanates that have been partially reacted with isocyanate-reactive ethylenic unsaturated compounds. Preferably, isocyanate-reactive ethylenic unsaturated compounds are those derived from α, β-unsaturated carboxylic acid, such as acrylates, methacrylates, maleinates, fumarates, maleimides, acrylamides, as well as vinylether, propenylether, alylether and compounds containing dicyclopentadienyl units. , which have at least one isocyanate-reactive group, especially preferred are acrylates and methacrylates with at least one isocyanate-reactive group. As hydroxy-functional acrylates or methacrylates, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide (meth) acrylates, polypropylene oxide mono (met) acrylates, polyalkylene oxide mono (meth) acrylates, poly (ε-caprolactone) mono (meth) acrylates are used) , such as, for example, Tone® M100 (Dow, USA), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the mono, di or hydroxy-functional tetra (meth) acrylates of alcohols, such as trimethylolpropane, glycerin, pentaerythrite, dipentaerythrite, ethoxylated, propoxylated or alkoxylated trimethylolpropane, glycerine, pentaerythrite, dipentaerythrite or their technical mixtures. In addition, compounds containing oligomeric or polymeric unsaturated acrylate and / or methacrylate groups are suitable individually or in combination with the aforementioned monomeric compounds. The proportion of isocyanates that have been partially reacted with isocyanate-reactive ethylenic unsaturated compounds in isocyanate component a) is 0 to 99%, preferably 0 to 50%, especially preferred 0 to 25% and even more preferred 0 to 15% .
    Eventually, it is also possible that the aforementioned isocyanate components a) contain fully or proportionally isocyanates, which are totally or partially reacted with blocking agents known to those skilled in the art of coating technology. As an example we refer as blocking agents: alcohols, lactams, oximes, malonic esters, alkylacetoacetates, triazoles, phenols, imidazoles, pyrazoles, as well as amines, such as, for example, butanonoxime, diisopropylamine, 1,2,4-triazole , dimethyl-1,2,4-triazole, imidazole, diethyl malonate, ethyl acetoacetate, acetonoxime, 3,5-dimethylpyrazole, ε-caprolactam, N-tert-butyl-benzylamine, cyclopentanecarboxyethyl ester or any mixtures of these blocking agents
    As components b) all polyfunctional isocyanate-reactive compounds can be used, which on average have at least 1.5 isocyanate-reactive groups per molecule.
    The isocyanate-reactive groups within the scope of the present invention are preferably hydroxy, amino or thio groups, especially preferred are hydroxy compounds.
    Suitable polyfunctional isocyanate-reactive compounds are, for example, polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
    Polyester polyols are suitable, for example, linear polyester diols or branched polyester polyols, which can be obtained by known methods from aliphatic, cycloaliphatic or aromatic di or polycarboxylic acids or their anhydrides with alcohols of OH> 2 functionality.
    Examples of such di or polycarboxylic acids or their anhydrides are succinic, glutaric, adipic, pyelic, submeric, azelaic, sebaceous, nonandicarboxylic, decandicarboxylic, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydrophthalic, as well as anhydrous, hydrolytic or trimellic acids. carboxylic acids, such as anhydrides of o-phthalic, trimellitic or succinic acids or mixtures of them.
    Examples of such suitable alcohols are etandiol, di, tri, tetraethylene glycol, 1,2-propandiol, di, tri, tetrapropylene glycol, 1,3-propandiol, butandiol-1,4, butandiol-1,3, butandiol-2,3, pentandiol-1,5, hexandiol-1,6, 2,2-dimethyl-1,3-propandiol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, octandiol-1,8, decandiol-1,10, dodecandiol- 1.12, trimethylolpropane, glycerin or mixtures with each other.
    Polyester polyols can also be based on natural raw materials such as castor oil.
    It is also possible to use polyester polyols based on homopolymerized or mixed polymerized lactones, as they can be obtained preferably by accumulation of lactones or mixtures of lactones, such as butyrolactone, ε-caprolactone and / or methyl-ε-caprolactone in hydroxy-functional compounds, such as alcohols of an OH> 2 functionality of the type mentioned above.
    Such polyester polyols preferably have an average molar mass of 400 to 4000 g / mol, especially preferred from 500 to 2000 g / mol. Its OH functionality is preferably 1.5 to 3.5, especially preferred 1.8 to 3.0.
    Suitable parbonatopolyols can be obtained by known methods by reacting carbonates or phosgens with diols or mixtures of diols.
    Suitable organic carbonates are dimethyl, diethyl and diphenylcarbonate.
    Suitable diols or mixtures comprise the alcohols of an OH> 2 functionality mentioned within the scope of the polyester segments, preferably 1,4-butandiol, 1,6-hexandiol and / or 3-methylpentandiol, or also polyester polyols can be reprocessed to polycarbonatopolyols.
    Such polycarbonatopolyols preferably have an average molar mass of 400 to 4000 g / mol, especially preferred from 500 to 2000 g / mol. The OH functionality of these polyols is preferably 1.8 to 3.2, especially preferred 1.9 to 3.0.
    Suitable polyether polyols are optionally polyaddition products, in the form of blocks, of cyclic ether in functional OH or NH initiator molecules.
    Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and mixtures thereof.
    As initiators, alcohols with an OH> 2 functionality mentioned in the scope of polyester polyols can be used, as well as primary or secondary amines and amino alcohols.
    Preferred polyether polyols are those mentioned previously exclusively based on propylene oxide or statistical copolymers or in block based on propylene oxide with other alkylene 1-oxides, where the proportion of alkylene 1-oxide is not greater than 80% in Weight. Poly (trimethylene oxide) s as well as mixtures of the polyols mentioned as being preferred are also preferred. Especially preferred are propylene oxide homopolymers, as well as statistical or block copolymers that have oxyethylene, oxypropylene and / or oxybutylene units, in which the ratio of oxypropylene units to the total amount of all oxyethylene, oxypropylene and oxybutylene is at least 20% by weight, preferably at least 45% by weight. Oxypropylene and oxybutylene comprise all respective linear and branched C3 and C4 isomers.
    Such polyester polyols preferably have an average molar mass of 250 to 10000 g / mol, especially preferred from 500 to 8500 g / mol and particularly preferably 600 to 4500 g / mol. Its OH functionality is preferably 1.5 to 4.0, especially preferred 1.8 to 3.1.
    In addition, they are also suitable as constituents of components b) as polyfunctional, isocyanate-reactive compounds, aliphatic, araliphatic or cycloaliphatic di, tri or polyfunctional alcohols with low molecular weight, that is, with molecular weights below 500 g / mol, and short-chain, that is, containing 2 to 20 carbon atoms.
    These may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,2-propandiol, 1,3-propandiol, 1,4-butandiol, neopentyl glycol, 2-ethyl-2-butylpropandiol, trimethylpentyl, diethylene, trimethylpandyl, diethylene positional isomers, 1,3-butylene glycol, cyclohexandiol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,2- and 1,4-cyclohexanediol, bisphenol A (2,2-bis (4-hydroxycyclohexyljpropane) hydrogenated, acid 2,2-dimethyl-3-hydroxypropanoic (2,2-dimethyl-3-hydroxypropyl ester) Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerin Suitable suitable high-alcohol alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
    As components c) one or more photoinitiators are used. These are generally initiators that are activated by actinic radiation that triggers a polymerization of the respective polymerizable groups. Photoinitiators are known and commercially available compounds, distinguishing between unimolecular (type I) and bimolecular (type II) primers. In addition, these initiators, depending on their chemical nature, are used for the anionic (or), cationic (or mixed) forms of the polymerizations mentioned above.
    Systems (type I) for radical photopolymerization are, for example, aromatic ketone compounds, for example benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michlers ketone), antrona and benzophenones halogenated or mixtures of the types mentioned. Equally suitable are initiators (type II), such as benzoyl and its derivatives, benzylacetals, acylphosphinoxides, for example, 2,4,6-trimethyl-benzoyl-diphenylphosphinoxide, bisacylphosphinoxides, phenylglyoxylic acid ester, camferquinone, alpha-aminoalkylphenols , alpha-, alpha-dialcoxyacetophenones, 1 - [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyloxime), variously substituted hexarylbisimidazoles (HABI) with suitable co-initiators, such as, for example, mercaptobenzoxazole, as well as alpha-hydroxyalkylphenones. Also, the photoinitiator systems described in EP-A-0223587 composed of a mixture of ammonium arylborate and one or more dyes can be used as a photoinitiator. Suitable as ammonium arylborate are, for example, tetra-butylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylate, tetrabutylammonium trinaftylbutylate, tetramethylammonium triphenylbenzylborate, tetra (n-hexyl) ammonium (sec-butyl-trifluentyl-trifluoroethyl) (4-tert-butyl) -phenylbutylborate, tetrabutylammonium tris- (3-fluorophenyl) -hexylborate and tetrabutylammonium tris- (3-chloro-4-methylphenyl) -hexylborate. Suitable dyes, for example, are new methylene blue, thionine, Basic Yellow, pinacinol chloride, Rhodamin 6G, galocyanine, ethyl violet, Victoria Blue R, Celestine Blue, quinaldine red, methyl violet, Brilliant Green, Astrazon Orange G, Darrow Red, Pyronin Y, Basic Red 29, Pyrphllium I, Safranin O, Cyanine and Methylene Blue, Azur A (Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19- 22, 1998).
    The photoinitiators used for anionic polymerization are generally from systems (type I) and are derived from first-line transition metal complexes themselves. We refer in this case to chromium salts, such as, for example, trans-Cr (NH3) 2 (NCS) 4- (Kutal et al, Macromolecules 1991, 24, 6872) or ferrocenyl compounds (Yamaguchi et al. Macromolecules 2000, 33, 1152). Another possibility of anionic polymerization is the use of dyes such as leuconitrile of ethyl violet or leuconitrile of malachite green, which can be polymerized by photolytic decomposition of cyanoacrylates (Neckers et al. Macromolecules 2000, 33, 7761). However, the chromophore is incorporated into the polymer, so that the resulting polymers are dyed.
    The photoinitiators used for cationic polymerization are essentially composed of three classes: arildiazonium salts, onium salts (here especially: iodonium, sulfonium and selenonium salts), as well as organometallic compounds. Phenyldiazonium salts can form a cation, under radiation in the presence or absence of a hydrogen donor, which initiates polymerization. The efficiency of the entire system is determined by the nature of the counterion used in relation to the diazonium compound. Preferred are SbF6-, AsF6- or PF6- which are not very reactive but are very expensive. For application in thin film coating, these compounds are, as a general rule, little suitable, since lighting releases nitrogen that reduces the surface quality (pinholes) (Li et al., Polymerie Materials Science and Engineering, 2001, 84 , 139). Widespread and commercially available in various forms are onium salts, especially sulfonium and iodonium salts. The photochemistry of these compounds was analyzed in the long term. The iodonium salts decompose homolytically after stimulation, producing a radical and a radical ion, which stabilize through the H abstraction and release a proton and then initiate cationic polymerization (Dektar et al. J. Org. Chem. 1990, 55, 639; J. Org. Chem., 1991, 56, 1838). This mechanism also allows the use of iodonium salts for radical photopolymerization. For this, the selection of the counterion is again fundamental. SbFθ, AsF6 or PFΘ are also preferred. Moreover, in this structural class, the selection of aromat substitution is relatively free and is determined by the availability of the initial modules for synthesis. In the case of sulfonium salts, these are compounds that decompose according to Norrish (II) (Crivello et al., Macromolecules, 2000, 33, 825). Also in the case of sulfonium salts, the selection of the counterion has a crucial significance, which is essentially reflected in the rate of hardening of the polymers. The best results are generally achieved with SbF6 salts. Since the proper absorption of the iodonium and sulfonium salts is <300 nm, these compounds have to be sensitized for photopolymerization with near UV or visible and short wave light. This is possible through the use of aromatics with high absorption, such as anthracene and derivatives (Gu et al., Am. Chem. Soc. Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or its derivatives ( Hua et al, Macromolecules 2001, 34, 2488-2494).
    It may also be advantageous to employ mixtures of these compounds. Depending on the type of radiation sources used for curing, the type and concentration of the photoinitiator must be adjusted by the methods known to those skilled in the art. More detailed information is described, namely in P. K. T. Oldring (Ed.), Chemistry & Technology of UV & EB Formulations For Coatings, Inks & Paints, Vol. 3, 1991, SITA Technology, London, S. 61-328.
    C) Preferred photoinitiators are mixtures of tetrabutylammonium triphenylhexylborate, tetra-butylammonium triphenylbutylate, tetrabutylammonium trinaptylbutylate, tetrabutylammonium tris- (4-tert-butyl) -phenylbutylate, tetrabutylammonium-trisyl-trisyl-3-trisyl-3-methyl-3-methyl-3 4-methylphenyl) -hexylborate and dyes, such as Astrazon Orange G, methylene blue, new methylene blue, Azur A, pyrilium I, safranin O, cyanine, galocyanine, Brilliant Green, methyl violet, ethyl violet and thionine.
    As components d) good results are achieved with high refraction acrylates as contrast components in photopolymer formulations, as described, for example in US 6,780,546.
    Therefore, it is preferred according to the invention, that the recording monomers included in the photopolymer formulations are acrylates, especially preferred with a refractive index n20D> 1.50. Particularly preferred are aromatic urethane acrylates with a refractive index ΠD> 1.50 at 589 nm, as described, for example, in WO2008 / 125199.
    Other objects of the present invention are the media for recording visual holograms obtainable under the use of fluorourethanes of formula (I), the use of such media as optical elements, images and representations or visual projections, as well as a process for recording a hologram using such media.
    The photopolymer formulations according to the invention may contain especially 15 to 79, preferably 30 to 60% by weight of matrix polymers, 5 to 50, preferably 10 to 40% by weight of engraving monomers, 1 to 10, preferably 1 up to 3% by weight of photoinitiators and 5 to 50, preferably 10 to 40% by weight of fluorourethanes and 0 to 10% by weight of other additives, where the sum of the constituents is 100% by weight.
    A second aspect of the invention relates to the production of a photopolymer formulation according to the invention in which matrix polymers, etching monomers, photoinitiators and fluorourethanes are mixed as plasticizers to the photopolymer formulation.
    A third aspect of the invention relates to a photopolymer formulation obtainable according to the process.
    A fourth aspect of the invention relates to a film, a film, a layer, a layer construction or a mold of the photopolymer formulation.
    The layers, layer constructions and molds of the photopolymer formulations according to the invention usually have Δn values, measured according to the methods described in the section "Measuring the holographic DE and Δn properties of holographic media by interference of two beams in orders reflectance "of Δn> 0.0120, preferably> 0.0130, especially preferred> 0.0140, particularly preferably> 0.0150.
    A fifth aspect of the invention relates to a photopolymer formulation for the production of optical elements, especially for the production of holographic elements and images.
    Also a subject of the invention is a process for the radiation of holographic media of the formulation according to the invention, in which the recording monomers are selectively polymerized with spatial resolution by means of electromagnetic radiation.
    This type of holographic media is suitable for the production of holographic optical elements after being subjected to holographic radiation, which have the function of an optical lens, a mirror, a deflecting mirror, a headlight filter, an diffraction, a waveguide, a light conductor, a projector disc and / or a mask. In addition, they also allow the production of holographic images or representations, such as, for example, for personal portraits, biometric representations in security documents or in general images or image structures for advertising, security codes, brand protection, brand management, labels, design elements, decorations, illustrations, trading cards, images and the like, as well as images that can represent digital data, among them also in combination with the products mentioned above.
    Certain fluorourethanes are known in the prior art. Thus, US 2003/105263 A1 describes fluorourethanes which are obtainable by reacting a polyisocyanate, containing biuret, isocyanurate, uretdione, polyurea, with a fluorinated alcohol. WO 03/023519 Describing fluorourethanes which are obtainable by reacting a polyisocyanate, containing biuret, with a fluorinated alcohol.
    Another aspect of the invention concerns a fluorourethane obtained through the reaction of a polyisocyanate, containing iminooxadiazindione or oxadiazadione, which has at least one group of free isocyanate, with an alcohol, in which the polyisocyanate and / or alcohol is replaced by least one fluorine atom.
    Finally, a fluorourethane according to the general formula (III) is also the object of the invention.
    in which m> 1 in <8 and FU, Rs, RΘ are hydrogen and / or organic radicals, independent of each other, linear, branched, cyclic or heterocyclic which are not substituted or possibly substituted by hetero atoms, and which have structural elements of iminooxadiazindione and / or oxadiazadione , in which at least two of the radicals FU, Rs, RΘ are simultaneously substituted by at least one fluorine atom. Examples:
    In the following the invention is explained in detail with examples.
    If there is no indication to the contrary, all percentage data refer to weight percent. Measurement methods:
    The indicated NCO values (isocyanate levels) were determined according to DIN EN ISO 11909.
    The measurement of the retraction index occurred according to one of the three methods presented below, depending on the quality of the compound sample:
    The measurement of the retraction index n with a wavelength of 405 nm (method A): The refractive index n, depending on the wavelength of the samples, were obtained from the transmission and reflection spectra. For that, films of samples with approximately 100 - 300 nm of density were coated by rotation in quartz glass cuvettes of a solution diluted in butyl acetate. The transmission and reflection spectrum of this layer were measured with a spectrometer from STEAG ETA-Optik, CD-Measurement System ETART and then the layer density and the spectral course of n was adjusted in the measured transmission and reflection spectra. This is done with the internal software of the spectrometer and additionally requires quartz glass substrate data, which was previously determined in a blind measurement.
    The measurement of the n20D refractive index with a wavelength of 589 nm (method B): A sample of the example compound was introduced into the Abbe refractometer and then the n20D was measured.
    The measurement of the n20D refractive index with a wavelength of 589 nm semi-concentrated solution (method C): A sample of the compound was diluted 50:50 (wt%) with N-ethylpyrrolidone and introduced into the Abbe refractometer and then n20D was measured. The approximate analyte refractive index was calculated, the n20D of N-ethylpyrrolidone was 1.4658. Measurement of DE and Δn properties of holographic media by interference of two beams in order of reflection
    The media produced were then analyzed for their holographic properties using a measuring device according to Figure 1:
    The beam of a He-Ne laser (emission wavelength 633 nm) was converted with the help of a spatial filter (SF) and together with the collimating lens (CL) into a homogeneous parallel beam. The final cross sections of the signal and the reference beam are defined through the diaphragms (I). The diaphragm opening diameter is 0.4 cm. Polarization-dependent light beam splitters (PBS) divide the laser beam into two coherent lasers of equal polarization. The power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW through the À / 2 plates. The powers were determined with semiconductor detectors (D) with the sample disassembled. The incidence angle (ao) of the reference beam is -21.8 °, the incidence angle (βo) of the signal beam is 41.8 °. The angles are measured from the normal of the sample towards the beam. According to Figure 1, ao has a negative number and βo has a positive number. At the sample site (media), the interference field of the two overlapping beams forms a network of lighter and darker bands that are located vertically in relation to the bisector of the two beams that fall on the sample (reflection hologram). The distance between the A bands, also called the graduation period, on the media is - 225 nm (assuming a media refractive index of -1.504).
    Figure 1 shows the geometry of a Media Testers (HMT) holography at À = 633 nm (He-Ne laser): M = mirror, S = closure, SF = spatial filter, CL = collimating lens, À / 2 = À2 plate , PBS = polarization sensitive beam splitter, D = detector, I = diaphragm, heat = -21.8 °, β0 = 41.8 ° are the angles of incidence of the coherent beams measured outside the sample (from the media) . RD = reference direction of the rotary table.
    With an experimental holographic structure as represented in Figure 1, the diffraction efficiency of the media was measured.
    Holograms were recorded on the media as follows: • Both shutters (S) were opened for exposure time t. • Afterwards, the media was left 5 minutes with the shutters (S) closed to diffuse the recording monomers that have not yet been polymerized.
    The engraved holograms were read as described below. The signal beam shutter remained closed. The reference beam shutter was open. The reference beam diaphragm was closed to a diameter of <1 mm. In this way, it was achieved that for all angles of rotation (Ω) of the media, the beam was always totally in the previously written hologram. The rotary table has now swept the angle area from Ωmin to Ωmax with a 0.05 ° angle pass, controlled by a computer. Ω is measured from the normal of the sample to the direction of the rotary table beam. The reference direction of the rotary table is obtained when, during the hologram recording, the angle of incidence of the reference and signal beam is equal according to the amount, that is, to = -31.8 ° and β0 = 31, 8th. Then, Ωre∞rding = 0 °. For ao = -21.8 ° and β0 = 41.8 °, ΩreCording is 10 °. In general, it is valid for the interference field during the recording ("recording") of the hologram:

    θo is the semi-triangle in the laboratory system outside the media and is valid during the recording of the hologram:

    In this case, θo = -31.8 ° is valid. In each swept rotational angle Ω, the powers of the beam transmitted in zero order were measured by means of the respective detector D and the powers of the beam diffracted in the first order by means of detector D. The diffraction efficiency is obtained in each swept angle Ω as the quotient:

    PD is the power in the diffracted beam detector and PT is the power in the transmitted beam detector.
    Through the process described above, Bragg's peak was measured, it describes the degree of diffraction efficiency η depending on the rotational angle Ω of the hologram that was recorded, and was saved on a computer. Additionally, the transmitted intensity of the order of zero against the rotational angle Ω was also recorded and saved on a computer.
    The maximum diffraction efficiency (DE = ηmax) of the hologram, that is, its peak value was determined with Ωre∞nstruction. Eventually, the position of the diffracted beam detector has to be changed to determine this maximum value.
    The contrast of the Δn refractive index and the d density of the photopolymer was determined using the Coupled Wave Theorie (see; H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 Page 2909 - Page 2947) at the peak measured Bragg and angle path of transmitted intensity. Bear in mind that due to photopolymerization, changes in density may occur, resulting in a deviation of the distance between the A 'band of the hologram and the orientation of the bands (slant) of the distance of the A band of the interference pattern and its orientation. In this way, the Ao 'angle or the respective ânguloreΩnstruction rotary table angle, which allows maximum diffraction efficiencies to be achieved, will also deviate from 0 or the respective ΩreΩrding. In this way, it also changes the condition of Bragg. This change is taken into account in the evaluation process. The evaluation process is described below:
    All geometric quantities, which refer to the engraved hologram and not to the interference pattern, are represented as streaked quantities.
    For the Bragg peak η (Ω) of a reflection hologram it is valid according to Kogelnik:
    with:

    For the reading of the hologram ("reconstruction"), the above is applied in a similar way:

    In Bragg's condition, "Dephasing" is DP = 0. It follows accordingly:

    The still unknown angle β'can be determined by comparing the Bragg condition of the interference field during the recording of the hologram and the Bragg condition during the reading of the hologram, assuming that only a change in density occurs. Then it follows:
    v the density of the network, S is the detuning parameter and ψ 'is the orientation (slant) of the refractive index network that was recorded, α'e β'corresponds to the angles ao and βo of the interference field during aggravation of the hologram , measured in the media and valid for the hologram network (according to the density variation), n is the mean refractive index of the photopolymer and was set to 1.504. À is the wavelength of the vacuum laser light.
    The resulting maximum diffraction efficiency (DE = ηmax) for S = 0:

    Figure 2 shows the transmitted power measured PT (right y axis) as a solid line applied over the ΔΩ angle detuning, the measured diffraction efficiency η (left y axis) as filled circles applied over the ΔΩ angle detuning (as long as the magnitude of the detector allows) and the adjustment of the Kogelnik theory as perforation line (left y-axis).
    The diffraction efficiency measurement data, the theoretical Bragg peak and the transmitted intensity are presented in Figure 2 applied on the centered rotational angle ΔΩ = Ωreconstruction - Ω = α'o -θ'o, also called angle detuning.
    Once DE is known, the theoretical Bragg peak shape according to Kogelnik is only determined through the density d 'of the photopolymer layer. Δn is corrected by DE for the indicated density d ', so that the measurement and theory of DE always correspond, d' is adjusted until the positions of the angles of the secondary minima of the theoretical Bragg peak corresponds with the angle positions of the first secondary maximums of the transmitted intensity and, in addition, there is also a correspondence between the total width of the theoretical Bragg peak at half the height (FWHM) and the transmitted intensity.
    Since the direction in which a reflection hologram also rotates during reconstruction using a Ω-Scan, the detector can only register a finite angle area for diffracted light, the Bragg peak of the wide holograms (d 'small ) is not fully registered with a Ω-Scan, only the central area with advantageous positioning of the detector. Therefore, a complementary form to the Bragg peak is used for the transmitted intensity, allowing to adjust the density d '.
    Figure 2 shows the representation of the Bragg peak η according to the Coupled Wave theory (perforated line), the degree of efficiency of the measured diffraction (filled circles) and the transmitted power (black solid line) on the ΔΩ angle detuning .
    For a formulation, this procedure was eventually repeated for different exposure times t in different media, to check with which average energy dose of the incident light beam during the hologram recording is transmitted DE for the degree of saturation. The average energy dose E results from the partial beam powers attributed to the two angles ao and βo (reference beam with Pr = 0.50 mW and signal beam with Ps = 0.63 mW), the exposure time t and the diameter diaphragm (0.4 cm) as shown below:

    The powers of the partial beams were adjusted so that in the media the same power density is reached in the angles ao and βo used. Substances used:
    Fluorlink E 10 / H is a reactive additive produced by Solvay Solexis based on fluorinated alcohol with an average molar weight of 750 g / mol.
    CGI-909 (tetrabutylammonium-tris (3-chloro-4-methylphenyl) (hexyl) borate, [1147315-11- 4]) is an experimental product produced by CIBA Inc., Basel, Switzerland. 1,8-diisocyanate-4- (isocyanatomethyl) octane (TIN) was produced as described in EP749958.
    The fluorinated alcohols used and the monofunctional isocyanates were purchased in the chemical trade, the polyisocyanates used (Desmodur H (HDI), Desmodur I (IPDI), Desmodur W, Desmodur LD, Desmodur N3400, Desmodur N3600, Desmodur N3900, Baymicron OXA) are commercial products from Bayer Materialscience AG, Leverkusen, Germany. 2,4,4-trimethylhexanes-1,6-diisocyanate, Vestanat TMDI, is a product of Evonik Degussa GmbH, Marl, Germany. Production of 2,2,2-trifluoroethyl- (6-isocyanatohexyl) carbamate
    In a 1 I distillation flask, 684 g of hexamethylenediisocyanate (HDI) were previously introduced at 80 ° C and 0.002 g of isoftalsâuredichlorid were added. 54.4 g of trifluoroethanol were slowly dripped and mixed until the NCO value was 43.2% by weight. The mixture was distilled off on a thin film evaporator and 47 g (= 47% of theory) of the title compound with an NCO content of 22.7% by weight were obtained. Production of 2,2,3,3,4,4,5,5-octafluoropentyl- (6-isocyanatohexyl) carbamate
    In a 1 I distillation flask, 399 g of hexamethylenediisocyanate (HDI) were previously introduced at 80 ° C and 0.002 g of isoftalsãuredichlorid were added. 73.4 g of 2,2,3,3,4,4,5,5-5 octafluoropentanol were slowly dripped and mixed until the NCO value was 39.4% by weight. The mixture was distilled off on a thin film evaporator and 40 g (= 40% of theory) of the title compound was obtained with an NCO content of 12.4% by weight. Example 1: Bis (2,2,2-trifluoroethyl) hexane-1,6-diylbiscarbamate
    In a 500 ml distillation flask, 0.07 g 10 of Desmorapid Z and 64.4 g of 6-diisocyanatohexane (HDI) were previously introduced and heated to 60 ° C.
    Then, 81.5 g of trifluoroethanol were dripped and the mixture was kept at 60 ° C until the isocyanate content had dropped to less than 0.1%. Then it was refrigerated. The product was obtained as a colorless solid.
    The examples described in table 1 presented below were produced according to the method indicated in example 1 in the indicated compositions.
    Table 1; Production and characterization of examples 2 - 224






























































    Example 225: 33,33,34,34-tetracosafluoro-20,20,22-trimethyl-6,17,26-trioxo- 7,16,27-trioxa-5,18,25-triazapentatriacontano-35-yl-butylcarbamate
    2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octandiol was previously introduced into a 250 ml distillation flask and 0.05 g of dibutylzinndilaurate (Desmorapid Z, Bayer Materialscience AG, Leverkusen, Germany) and were heated to 60 ° C. 18.7 g of n-butylisocyanate was added in portions and stirred for 3 h at 60 ° C. Then, 19.9 g of 2,4,4-trimethylhexane-1,6-diisocyanate (TMDI) were dripped and the mixture was maintained at 60 ° C until the isocyanate content had dropped to less than 0.1%. Then it was refrigerated and the product was obtained as a colorless oil. The refractive index determined according to method B is n20D = 1.4131. Example 226: 23- (8,8,9,9,10,10, ll, ll, 12,12,13,13-dodecafluoro-5,16-dioxo- 6,15-dioxa-4,17-diazahenicos- 1-il) - 9,9,10,10,11,11,12,12,13,13,14,14,29,29,30,30,31, 31,32,32,33,33,34 , 34-tetracosafluoro-6,17,26-trioxo-7,16,27-trioxa-5,18,25-triaza-5 pentatriacontano-35-yl-butylcarbamate
    2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1,8-octandiol was previously introduced into a 100 ml distillation flask and 0.01 g of dibutylzinndilaurate (Desmorapid Z, Bayer Materialscience AG, Leverkusen, Germany) and heated to 60 ° C. 3.63 g of n-butylisocyanate was added in portions and stirred for 3 h at 60 ° C. Then, 3.08 g of 1,8-diisocyanate-4- (isocyanatomethyl) octane (TIN) were dripped and the mixture was maintained at 60 ° C until the isocyanate content had dropped to less than 0.1%. Then it was refrigerated and the product was obtained as a colorless oil. The refractive index determined according to method A is n = 1.4200. Media production
    To check the optical properties, the media described below were produced and measured optically: Production of polyol components:
    In a 1 I flask, 0.18 g of tin octoate, 374.8 g of ε-caprolactone and 374.8 g of a difunctional polytetrahydrofuran-polyether-polyol (equivalent weight 500 g / mol OH) were previously introduced and heated up to 120 ° C maintained at this temperature until the solids content (proportion of non-volatile components) is 99.5% by weight above. Then it was refrigerated and the product was obtained as a waxy solid. Production of urethane acrylate 1: phosphorothioyltris (oxybenzol-4,1-diylcarbamoyl-oxyethane-2,1-diyl) trisacrylate
    In a 500 ml distillation flask, 0.1 g of 2,6-di-tert-butyl-4-methylphenol, 0.05 g tin dibutyl dilaurate (Desmorapid Z, Bayer Materialscience AG, Leverkusen, Germany) were previously introduced ), as well as 213.07 g of a 27% solution of tris (p-isocyanatophenyl) thiophosphate in ethyl acetate (Desmodur® RFE, product of Bayer Materialscience AG, Leverkusen, Germany) and heated to 60 ° C. Then, 42.37 g of 2-hydroxyethylacrylate were dropped and the mixture was maintained at 60 ° C until the isocyanate content had dropped to less than 0.1%. Then it was refrigerated and the ethyl acetate was completely removed in vacuo. The product was obtained as a semi-crystalline solid. Production of urethane acrylate 2: 2 - ({[3- (methylsulfanyl) phenyl] carbamoyl} oxy) -propylprop-2-enoate
    In a 250 ml distillation flask, 0.05 g of 2,6-di-tert-butyl-4-methylphenol, 0.02 g of Desmorapid Z, 26.8 g of 3- (methylthio) phenylisocyanate were previously introduced into 50 g of ethyl acetate and heated to 60 ° C. Then, 21.1 g of 2-hydroxypropylacrylate were dripped and the mixture was maintained at 60 ° C until the isocyanate content had dropped to less than 0.1%. Then, the ethyl acetate was removed by distillation at 5 mbar and refrigerated. The product was obtained as a light yellow liquid. Media 1:
    3.82 g of polyol components produced as described above were mixed with 2.50 g of phosphorootioyltris (oxybenzol-4,1-diylcarbamoyl-oxyethane-2,1-diyl) trisacrylate (urethane-acrylate 1), 2.50 g 2,2,2-trifluoroethylhexylcarbamate (example 4), 0.10 g of CGI 909 (experimental product from Giba Inc., Basel, Switzerland), 0.01 g of methylene blue and 0.35 g of N-ethylpyrrolidone at 60 ° C, in order to obtain a clear solution. Then it was cooled to 30 ° C, 0.71 g of Desmodur® N3900 (commercial product from Bayer Materialscience AG, Leverkusen, DE, polyisocyanate based on hexanediisocyanate, iminooxa-diazindione ratio of at least 30%, content of NCO: 23.5%) and was mixed again. Finally, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product from Momentive Performance Chemicals, Wilton, CT, USA) was added and mixed again. The liquid mass obtained was placed on a glass plate and covered with a second glass plate, which was maintained at a distance of 20 pm through a spacer. This sample was left for 12 hours at room temperature and allowed to set.
    Media 2-13 were produced in a manner analogous to the examples shown in table 1. Table 2 indicates the illustrative compound that was contained in which photopolymer formulation and with what content. The Δn values determined for the produced photopolymer formulations are also summarized in table 2. Media 14:
    3.40 g of polyol components produced as described above were mixed with 2.00 g of phosphorootioyltris (oxybenzol-4,1-diylcarbamoyl-oxyethane-2,1-diyl) trisacrylate (urethane-acrylate 1), 2.00 g 2 - ({[3- (methylsulfanyl) phenyl] - 'carbamoyl} oxy) -propylprop-2-enoate (urethane acrylate 2), 1.50 g of 2,2,2-trifluoroethyl-hexylcarbamate (example 4) , 0.10 g of CGI 909 (experimental product from Ciba Inc., Basel, Switzerland), 0.01 g of methylene blue again and 0.35 g of N-ethylpyrrolidone at 60 ° C, in order to obtain a clear solution. Then it was cooled to 30 ° C, 0.64 g of N3900 (commercial product from Bayer Materialscience AG, Leverkusen, DE, polyisocyanate based on hexanediisocyanate, iminooxa-diazindione ratio of at least 30%, NCO content was added : 23.5%) and was mixed again. Finally, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product of the company Momentive Performance Chemicals, Wilton, CT, USA) were added and mixed again. The liquid mass obtained was placed on a glass plate and covered with a second glass plate, which was maintained at a distance of 20 pm through a spacer. This sample was left for 12 hours at room temperature and allowed to set.
    Media 14-70 were produced in a similar way to the examples presented in Table 1. In Table 3, it is indicated which illustrative compound was contained in which photopolymer formulation and with what content. The Δn values determined for the produced photopolymer formulations are also summarized in table 3. Comparative media I:
    8.89 g of the polyol components produced as described above were mixed with 3.75 g of phosphorothioyltris (oxybenzol-4,1-diylcarbamoyl-oxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 0.15 g of CGI 909 (experimental product of Ciba Inc., Basel, Switzerland), 0015 g of methylene blue again and 0.53 g of N-ethylpyrrolidone at 60 ° C, in order to obtain a clear solution. Then, they were cooled to 30 ° C, 1.647 g of Desmodur® N 3900 (commercial product from Bayer Materialscience AG, Leverkusen, Germany, polyisocyanate based on hexandiisocyanate, iminooxadiazindione ratio at least 30%, NCO content: 23, 5%) and was mixed again. Then, 0.009 g of Fomrez UL 28 (urethanization catalyst, commercial product from Momentive Performance Chemicals, Wilton, CT, USA) was added and mixed again. The liquid mass obtained was placed on a glass plate and covered with a second glass plate, which was maintained at a distance of 20 pm through a spacer. This sample was left at room temperature for 12 hours and allowed to harden. Comparative media II:
    3.82 g of the polyol components produced as described above were mixed with 2.50 g of phosphorothioyltris (oxybenzol-4,1-diylcarbamoyl-oxyethane-2,1-diyl) trisacrylate (urethane acrylate 1), 2.50 g propylenocarbonate (comparative example II), 0.10 g of CGI 909 (experimental product from Ciba Inc., Basel, Switzerland), 0010 g of new methylene blue and 0.35 g of N-ethylpyrrolidone at 60 ° C, in order to obtain a clear solution. Then, it was cooled to 30 ° C, 0702 g of Desmodur® N3900 (commercial product of Bayer Materialscience AG, Leverkusen, DE, polyisocyanate based on hexanediisocyanate, iminooxa-diazindione ratio of at least 30%, NCO content : 23.5%) and was mixed again. Finally, 0.022 g of Fomrez UL 28 (urethanization catalyst, commercial product from Momentive Performance Chemicals, Wilton, CT, USA) was added and mixed again. The liquid mass obtained was placed on a glass plate and covered with a second glass plate, which was maintained at a distance of 20 pm through a spacer. This sample was left for 12 hours at room temperature and allowed to set.
    The comparative media III-IV were produced in a similar way to the comparative examples presented in table 2. Comparative media VI:
    4.66 g of the polyol components produced as described above were mixed with 2.00 g of phosphorothioyltris (oxybenzol-4,1-diylcarbamoikoxyethane-2,1 - diyl) trisacrylate (urethane acrylate 1), 2.00 g of 2- ({[3- (methylsulfanyl) phenyl] - carbamoyl} oxy) -propylprop-2-enoati (urethane acrylate 2), 0.10 g of CGI 909 (experimental product of the firm. Ciba Inc., Basel, Switzerland), 0.010 g of methylene blue again and 0.35 g of N-ethylpyrrolidone at 60 ° C until a clear solution is obtained. Then, they were cooled to 30 ° C and 0.87 g of Desmodur® N 3900 (commercial product from Bayer Materialscience AG, Leverkusen, Germany, polyisocyanate based on hexandiisocyanate, proportion of at least 30% iminooxadiazindione, content of NCO : 23.5%) and was mixed again. Then, 0.006 g of Fomrez UL 28 (urethanization catalyst, commercial product from Momentive Performance Chemicals, Wilton, CT, USA) was added and mixed again. The liquid mass obtained was placed on a glass plate and covered with a second glass plate, which was maintained at a distance of 20 pm through a spacer. This sample was left for 12 hours at room temperature and allowed to set.
    Table 2: Holographic evaluation of selected examples in the formulation with 25% urethane acrylate 1 and 25% additive (fluorinated urethane).


    The values described for Δn were achieved with doses of 4-32 mJ / cm2.
    The values obtained for the holographic property Δn of holographic media reveal that commercial additives used in comparative media are less suitable for application in holographic media. On the contrary, the urethanes according to the invention are very suitable in media 1 to 13 for the production of holographic media due to the high value of Δn.
    Table 3: Holographic evaluation of selected examples in the formulation with 20% by weight urethane acrylate 1.20% by weight urethane acrylate 2 and 15% by weight additive (fluorinated urethane).


    The values described for Δn were achieved with doses of 4-32 mJ / cm2.
    The values obtained for the holographic Δn property of holographic media reveal that the fluorinated urethanes according to the invention are very suitable in media 14 to 70 for the production of holographic media due to the high value of Δn.
    权利要求:
    Claims (12)
    [0001]
    1. Photopolymer formulation comprising matrix polymers, recording monomers and photoinitiators, CHARACTERIZED by the fact that the photopolymer formulation still comprises fluorourethanes as plasticizers, in which the matrix polymers comprise polyurethanes and in which the photopolymer formulation essentially consists of 15 to 79% by weight of matrix polymers, 5 to 50% by weight of acrylate etching monomers, with a refractive index of n20D> 1.50, 1 to 10% by weight of photoinitiators, between 5 and 40% by weight fluorourethanes and 0 to 10% by weight of other additives, where the sum of the constituents is 100% by weight.
    [0002]
    2. Photopolymer formulation according to claim 1, CHARACTERIZED by the fact that fluorourethanes comprise compounds having the formula (I):
    [0003]
    3. Photopolymer formulation according to claim 2, CHARACTERIZED by the fact that R1 represents an organic radical with at least one fluorine atom.
    [0004]
    4. Photopolymer formulation according to claim 2, CHARACTERIZED by the fact that R1 comprises 1-20 CF2 groups and / or one or more CF3 groups, R2 comprises a C1-C20 alkyl or hydrogen radical, and R3 comprises a C1 radical -C20 alkyl or hydrogen.
    [0005]
    5. Photopolymer formulation according to claim 2, CHARACTERIZED by the fact that R1 comprises 1-10 CF2 groups and / or one or more CF3 groups, R2 comprises a C1-C10 alkyl or hydrogen radical, and R3 comprises a C1 radical -C10 alkyl or hydrogen.
    [0006]
    6. Photopolymer formulation according to claim 2, CHARACTERIZED by the fact that R1 comprises 1-8 CF2 groups and / or one or more CF3 groups.
    [0007]
    7. Photopolymer formulation according to claim 1, CHARACTERIZED by the fact that fluorourethanes comprise structural elements of uretdione, isocyanurate, biuret, allophanate, polyurea, oxadiazadione and / or iminooxadiazindione and / or mixtures of these structural elements.
    [0008]
    8. Photopolymer formulation according to claim 1, CHARACTERIZED by the fact that fluorourethanes have a refractive index n20D <1.4500.
    [0009]
    9. Photopolymer formulation, according to claim 1, CHARACTERIZED by the fact that fluorourethanes have a refractive index n20D <1,4300.
    [0010]
    10. Photopolymer formulation according to claim 1, CHARACTERIZED by the fact that fluorourethanes have a fluorine content of 10-80% by weight.
    [0011]
    11. Photopolymer formulation according to claim 1, CHARACTERIZED by the fact that fluorourethanes have a fluorine content of 17.5-65% by weight.
    [0012]
    12. Process for displaying holographic media, CHARACTERIZED by the fact that it comprises the photopolymer formulation, as defined in claim 1, in which the process comprises selectively polymerizing the recording monomers with spatial resolution by electromagnetic radiation.
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    法律状态:
    2019-01-08| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-06-30| B09A| Decision: intention to grant|
    2020-10-20| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 02/11/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP09013770.4|2009-11-03|
    EP09013770|2009-11-03|
    PCT/EP2010/066591|WO2011054795A1|2009-11-03|2010-11-02|Fluorourethane as an additive in a photopolymer formulation|
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